Azodyestuffs



Patented Nov. 27, 1934 AZODYESTUFFS Carl Taube, Leverkusen-Wiesdorf,Germany, as:

signer to General Aniline Works, Inc New. York, N. Y., aoorporationofDelaware N Drawing. Application March. 17, 1932, Serial No. 599,591.In Germany March-25, 1931 10 Claims. (G1. 260- 72) The present inventionrelates to azodyestufis, more particularly it relates to dyestuffs whichmay be represented by the probable general formula;

wherein R, stands for the radical of a diazotization'component of thebenzene or naphthalene series, that means, for a benzene or naphthalenenucleus which may be substituted, for example, by a sulfonic acid group,a carboxylic acid group, a halogen atom, a hydroxy group, an alkoxygroup, an alkyl group and a. nitro group, M stands for the radical of acoupling component, containing a methylene group capable of coupling andcontaining a diazotizable amino group that means an amino group attachedto an aromatic nucleus, X stands for alkyl or hydroxyalkyl in which thehydroxy group may be esterified by sulfuric acid, such as methyLethyl,propyl, isopropyl, for the group CI-I2CH2OH, or for the group-CHzCH2O-SO3H, Y stands for i hydrogen, a benzene nucleus, or for anacyl group, such as an acetyl group or a benzoyl group, n stands for thenumbers one or two, and wherein the nucleus R1 may be substituted by asulfonic acid group. i

5 As coupling components containing a methylene group capable ofcoupling and a diazotizable amino group, there may be mentioned by wayof example 1 (aminophenyl) 3-methyL-5-pyrazolone, l-(aminophenyl)5-pyrazolone-3-carboxylic acid, Bz-aminomethylketol of the formula:

aN- J! V OH:

Bz-aminosulfazone of the formula:

a yellowish red "coloration) and diazotized withBz-amino-znl-dihydroxyquinoline of the formula:

"Bz-amino-acetoacetic acid arylamides, such as amino-acetoacetic acidanilide, amino-acetoacetic 5 T acid chloroanilide, amino-acetoaceticacid tolu idide, amino acetoacetic acid anisidideor other derivatives'ofp ketoaldehydeafor instance, 132,- amino-1.3-diketohydroindene oftheformula:

The new Products are obtainableby couplinga diazotized amine of thebenzene or naphthalene series with a compoundcontaining a methylene,group capable of coupling and a cliazotizable amino group, furtherdiazotizing the product thus obtained, combining with an 1-amino-2-naphtholether or a derivative thereof, again di azotizing and finallycoupling in pyridine solution with a 1 amino-8-naphthol-sulfonic acidoran N-acyl derivative thereof. 35

My new dyestuffs are in the form of their alkali metal salts generallydark powders. They are soluble in water and dye the cellulosic. fibregen-- erally green shades of good fastness properties.

.The ,-invention is illustrated by the following examples, without beinglimited thereto:

Example 1.-10 parts by weight of 2.5-dichloroaniline-4-sulfonic acid arediazotized in the customary mannerwith 2 .48 parts by weight ofsodiumnitrite andihydrochloric acid, and after neutralizing with sodiumacetate, the diazo compound is coupled with 8.3 parts by weight ofl-(m-aminophenyl)-3-methyl-5-pyrazolone. The yellow dyestuff isisolated, dissolved'in dilute sodium carbonate solution and diazotizedwith 2.5 parts by weight of sodium nitrite and hydrochloric acid. Thediazonium salt is coupled after filtration with 10 parts by weight offinely divided 1-amino-2- naphtholethylether-6-sulfonic acid, the brownproduct is dissolved in dilute caustic soda (giving excess sodiumnitrite and hydrochloric acid, the diazoniumsalt is isolated and coupledwith 15 parts by weight of 1-acetylamino-8-naphthol-3.6- disulfonic acidin the presence of pyridine, The no polyazodyestuff having in the freestate the following formula? is isolated and dried in the customarymanner. It is a black powder, readily soluble in water with a greencoloration; cotton is dyed by the customary dyeing processes a clearbluish green shade.

Example 2.--='.05 parts by weight of o-sulfanilic acid are diazotized inthe customary manner with 2 parts by weight of sodium nitrite andhydrochloric acid, and, after neutralizing with sodium acetate, coupledwith 6.6 parts by weight of the dyes cotton a yellowish green shade.

Example 3.10 parts by weight of 2-naphthylamine-S-sulfonic acid arediazotized in the customary manner with 2.82 parts by weight of sodiumnitrite and hydrochloric acid, and; after neutralization with sodiumacetate, are coupled with 9.4 parts by weight of l-(m-aminophenyl)3-methyl-5-pyrazolone. The yellow dyestuff is tized with 2.8 parts byweight of sodium nitrite and hydrochloric acid, and, afterneutralization with sodium acetate, coupled with 12 parts by weight of1-amino-2-naphtholethylether-6-sulfonic acid. The product is filtered,dissolved in dilute caustic soda and diazotized with 3.2 parts by weightof sodium nitrite and hydrochloric acid. The diazonium salt is isolatedand coupled with 18 parts by weight of 1-acetylamino-8-naphthol-3.6-disulfonic acid in the presence of pyridine. The dyestufi having inthe free state the following formula: 1

oozm H0 N110 COB dyes cotton deep green shades.

Example 4.10 parts by weight of 4-chloro-2- sulfanilic acid arediazotized in the customary manner with 3.32 parts by weight of sodiumnitrite and hydrochloric acid, and, after neutralization with sodiumacetate, are coupled with 11.1 parts by weight of l-(m-aminophenyl)-3-methyl-5- pyrazolone. The dyestuff is isolated, diazotized with 3.3parts by weight of sodium nitrite and hydrochloric acid, and, afterneutralization with sodium acetate, coupled with 14 parts by weight of1-amino-2-naphtholethylether-6-sulfonic acid.

NHOGOHa' SO H HOaS The product is isolated, dissolved in dilute causticsoda and diazotized with 4.5 parts by weight of sodium nitrite andhydrochloric acid. The diazonium salt is coupled after filtration in thepresence-of pyridine with 25 parts by weight of 1- (2.4"-di'chlorobenzoyl) -amino-8-naphthol-4.6- disulfonic acid. Thedyestufi having in the free state the following formula:

(')CzH| H? 111E HOS I I \N/ S0111 SOaH filtered, dissolved in dilutecaustic soda, diazo dyes cotton a clear green shade.

rgesasse Example fie--10 parts by weight of Z-nitroisultanilic: acid arediazotized in the customarymanner with 2.7 parts by weight of sodiumnitrite and hydrochlorid acid, and, after neutralization with sodiumacetate, coupled with 9 parts by weight of 1- (m-amino-phenyl) -3-methyl-5-py-- razolone. The dyestuff is isolated, dissolved in SOzH dyescotton clear yellowish green shades.

Similar combinations are produced when instead. of the componentsspecified in the examples there is used as the first componentp-anisidine-o-sulfonic acid (OCH3=1), aniline- 2.5-disulfonic acid,4-,toluidine-2-sulfanilide, 4- toluidine-S-sulfonic acid,m-xylidine-o-sulfonic acid or 4-acetamino-2-sulfanilic acid, as thesecond component l (paminophenyl) -3-methy1-5- pyrazolone, maminoacetoacetic anilide or l-(m-.

1, memos.

wherein R stands for the radical of a diazotization component of thebenzene ornaphthalene series, M stands for the radical of a couplingcomponent containing a methylene group capable of coupling and adiazotizable amino group, X stands for alkyl or hydroxyalkyl in whichthe hydroxy group maybe esterifled by sulfuric acid, Y-stands forhydrogen or an acyl group, "n" stands for the numbers one or two, andwherein the nucleus R1 may be substituted by a sulfonic acid group,being in form of their alkali metal salts generally water soluble darkpowders, dyeing the cellulosic fibre generally green shades of goodfastness properties,

2. Azodyestuffs of the probable general formula: i

wherein R stands for the radical of a diaz-otization component of thebenzene or naphthalene series, M stands for the radical of an(amino-phenyl)-pyrazolone or for the radical of V Y I so its wherein Rstands for a benzene or naphthalene nucleus which may be substituted bysubstituents selected from the group consisting of the sulfonic acidgroup, the carboxylic acid group, a halogen atom, the hydroxy group, analkoxy group, an alkyl grounand the nitro' group, fM" stands for theradical of an (amino-phenyl)-pyrazolone or for the radical of anamino-aceto-acetic acidarylamide, X stands for alkyl or hydroxyalkyl inwhich the hydroxy group may be esterified by sulfuric acid, Y stands forhydrogen or an acyl group, .fn stands for the numbers one or two, andwherein the nucleus R1 may be substituted by asulfonic acid group, beingin form of their alkali metal salts generally water soluble darkpowders, dyeing the cellulosic fibre generally green shades of goodfastness properties.

4. The azodyestuff having in its free state the wherein R is the radicalof a diazo component of following formula: the benzene or naphthaleneseries which may have com. no m s-o -0113 being in form of its alkalimetal salts a water substituted thereon sulfonic acid and halogen 90soluble black powder dyeing cotton clear bluish groups, X stands forhydrogen or a sulfonic acid green shade. group, Y stands for hydrogen,abenzene nucleus 5. The azodyestuff having in its free state the or anacyl group and n stands for the numbers 1 following formula: or 2. 0H3S0311 95 l 8. A trisazo dye having the probable general being in form ofits alkali metal salts a waterformula:

(I) 01H; HO NH-acyl N=N N: S H /CO\ I N OI )2 T ]"0 no I t N i $0311 (503H 7 Ha v soluble dark powder, dyeing cotton yellowish 9. A trisazo dyehaving the probable general 40 green shades. formula: i r 1 L I a. 00 gN=N\ --\l-(soln i 12o a 3113 6. The azodyestuff having in its free statethe 10. A process for producing trisazo dyes which 125 followingformula: comprises coupling a diazotized amine of the ben- H 00,11, no111700-03: V a 1 N-N N-N I N=N- J 3==o l v a 130 nae-0 N i Hms so.n

No, 80 11 a p l zene or naphthalene series, which may be further 335substituted by sulphonic acid and chlorine groups, g withl-(m-amino-phenyl)-3-methyl5-pyrazo- 03H lone, diazotizing the resultingamino azo com being in form of its alkali metal salts a waterpound andcoupling it with 1-amino-2-ethoxysoluble dark powder, dyeing cotton,yellowish naphthalene which may have substituted there- 4 green shades.Y on a sulfonic acid group, diazotizing the resulting '7. A trisazo dyehaving the following general amino-disazo compound and coupling it witha formula; member selected from the group consisting of RN=NOH N' Y I C/o N aminonaphtholsulfomc acids and N-substituted' 1 5 derivativesthereof. CARL ,TAUBE.

